Process for breaking petroleum emulsions employing certain polyepoxide modified oxyalkylation derivatives, said derivatives obtained in turn by oxyalkylation of phenol-aldehyde resins



PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN PGLYEPOXIDE MODIFIED OXYALKYLATION DERIVATIVES, SAID DERIVATIVES OBTAINED IN TURN BY OXYALKYLATION OF PHENOL-ALDEHYEE RESINS Melvin De Groote, University City, and Kwan-Ting Siren, Brentwood, Mo., assignors to Pen-elite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application November 19, 1953, Serial No. 393,222

2 Claims. (Cl. 252-331) The present application is a continuation-in-part of our co-pending applications, Serial No. 343,804, filed March 20, 1953, and Serial No. 349,972, filed April 20, 1953. The first of said copending applications relates to processes for breaking petroleum emulsions of the water-in-oil type employing a demulsifier including the reaction products of (A) certain oxyalkylated phenolaldehyde resins, therein described in detail, and (B) certain phenolic polyepoxides and cogenerically associated compounds formed in their preparation, also therein described in detail, the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) to one mole of (B).

The second of the aforementioned .co-pending applications is comparable to the above application, Serial No. 343,804, except that the polyepoxide employed is a non-aryl hydrophile polyepoxide which is therein described in detail.

Note that in both patent applications the molal ratio of oxyalkylated resin to polyepoxide is 2 to 1.

In our 2 co-pending applications, Serial Nos. 393,221 and 393,223, the same situation applies except that the molar ratio is 4 to 3 instead of 2 to 1. Co-pending application, Serial No. 393,221, employs the same type of polyepoxide as in Serial No. 343,804. Likewise, copending application, Serial No. 393,223, employs the same type of epoxide as co-pending application, Serial No. 349,972.

In the present application the molal ratio again is 4 to 3 and not 2 to l and involves both type of polyepoxides. Stated another way, the hydrophobe polyepoxide described in Serial No. 343,804 is employed first in a 2 to 1 ratio, and then 2 moles of this larger molecule are united by one mole of the hydrophile polyepoxide described in Serial No. 349,972. Thus, it is obvious that the present application employs the products described in Serial No. 343,804 as an intermediate. For this reason much of the text is identical with that found in Serial No. 343,804 but that part of the text which describes the hydrophile polyepoxide in Serial No. 349,972 also appears in the present description.

Thus the present invention relates to processes for breaking petroleum emulsions of the water-in-oil type employing a demulsifier including the reaction product of (A) certain oxyalkylated phenol-aldehyde resins, here inafter described in detail, and (B) certain phenolic polyepoxides and cogenerically associated compounds formed in their preparation, hereinafter described in detail, further reacted with (C) certain non-aryl hydrophile polyepoxides, also hereinafter described in detail. The reactants A and B are reacted in the molar proportion of 2 to 1 respectively to form an intermediate (ABA) and this intermediate is reacted with (C) in the molar proportion of 2 to 1 respectively to produce the final reaction product (ABACABA).

2,792,355 Patented May 14, 1957 These products are obtained from certain hydroxylated heat-stable resins, which, since they are heat-stable, are also susceptible to reaction in various ways to yield products other than oxyalkylation products, such aswherein R is a comparatively small alkyl radical, such as methyl, ethyl, propyl, etc. In light of this fact, i. e., that the reaction products of the selected resins herein described and the epoxides are apparently new per se and may be utilized in a manner other than specifically described herein, it is obvious they represent part of the instant invention. The resultants obtained by reaction between the resinous materials and the imine type reactant exemplify new compounds having properties usually found in cationic surface-active agents and can be used for the purposes for which these materials are commonly employed. The materials so obtained are still susceptible to oxyalkylation with an alkylene oxide, such as ethylene oxide, propylene oxide, etc., and can be reacted with these oxides in the same manner as herein described in connection with the resinous materials which have not been subjected to the intermediate reaction with an imine.

Actually any reference in the claims or specification to the property of being oxyalkylation-susceptible might just as properly be characterized as being iminereactive or for that matter as oxyalkylation-susceptible and imine-reactive.

The products obtained by reaction between the oxyalkylated derivatives and the polyepoxides are obviously acylation-suscep'tible as well as being oxyalkylation-susceptible. For instance, they could be subjected to reaction with alkylene oxides different than those previously described as, for example, styrene oxide. These derivatives additionally must have a number of aliphatic hydroxyl groups. Such aliphatic hydroxyl groups as differentiated from phenolic hydroxyl groups present in one of the initial reactants are particularly susceptible to acylation with various carboxylic and non-carboxylic acids. They may be reacted with detergent-forming monocarboxy acids, particularly higher fatty acids, which are saturated or unsaturated, as well as polycarboxy acids, such as phthalic anhydride, maleic anhydride, etc. Similarly, they can be reacted with maleic acid or a fractional maleic acid ester, such as the mono-octyl ester of maleic acid, and the neutral ester obtained can be reacted with sodium bisulfite so as to introduce a sulfonic group.

Notwithstanding the fact that subsequent data will be presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in mind. The polyepoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative, or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

As far as the hydrophobe polyepoxides go and par, ticularly the hydrophobe diglycidyl ether-s, used in the 3 a first stage or the preparation of the intermediate, if it were benzene, toluene, dioxane, various ketones, chlorinated not for the expense involved in preparing and purifying solvents, dibutyl ether, dihexyl ether, ethyleneglycol dithe monomer we would prefer it to any other form, i. e., ethylether, diethyleneglycol diethylether, and dimethoxyin preference to the polymer or mixture of polymer'and tetraethyleneglycol. monomer. 5 The expression epoxy is not usually limited to the Stated another Way We would P r to use materials 1 ,2-epoxy ring. The 1,2-epoxy ring is sometimes referred of the kind described as first-stage reactants, for example, to as the oxirane ring to distinguish it from other epoxy U- Patent dated November 1950- rings. Hereinafter, theword epoxy, unless indicated Sald Patent described Compounds having the general otherwise, will be used to means the oxirane ring, i. e.,

formula the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to p v as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega posiwherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 to 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings and employed for combination with the oxya lkylated phenolaldehyde resin are characterized by the following formula and cogenerically associated compounds formed in their tion. This is a departure, of course, from the standpoint of a strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2-3,4-diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the result or reaction product described preparation: in the previous text, it may be important to note that H in H, l l 1 H 2 i 1n 1 H, H H2 on in which R represents a divalent radical selected from somewhat similar compounds, generally of much higher the class of ketone residues formed by the elimination of molecu r eig ha e been described as complex resinthe ketonic oxygen atom and aldehyde residues obtained 011s epoxides which are polyether derivatives of polyby the elimination of the aldehydic oxygen atom, the hy r Phenols Containing an average of more than 0116 divalent radical epoxide group per molecule and free from functional H H groups other than epoxide and hydroxyl groups. See g-g U. S. Patent No. 2,494,295, dated January 10, 1950, to

Greenlee. The compounds here included are limited to the monomers or the low molal members of such series 0 and generally contain two epoxide rings per molecule and U may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not resins and have certain solubility characteristics not inherent in resins. Note, for example, that said U. S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin. The intent in the present instance in a comparable example would be to use a sulfonamide (not a sulfonamide resin) and obtain a material which does not have the characteristics of an ordinary varnish resin or the like, i. e., is permanently soluble, and stays soluble generally as a liquid of ordinary viscosity, or as a'thick viscous liquid and may be a thermoplastic solid, and additionally even may be water-soluble.

the divalent radical, the divalent sulfone radical, and the divalent mono'sulfide radical S, the divalent radical and the divalent disulfide radical S-S-; and R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R', R", and R represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; 11 represents an integer including zero and l, and n represents Whole number not greater than 3. The above menmolal polymers thereof, it becomes obvious'the reaction tioned compounds and those associated compounds can take place with any one of a number of oxyalkylated formed in their preparation are thermoplastic and organic resins which are still oxyalkylation-susceptible. There is 'solveflt'soluble- RefemnFe belng thermoplastic C available considerable literature, particularly patent literacteflzes proclllcts as 9 8 llqllids at Ordinary p ature dealing with oxyalkylated resins of the kind herein (mire \leadlly conveftlble t0 liquids y m y heating employed for reaction with the selected polyepoxides. belowithe P011111 Py y thus differentiates 1 6 These will be referred to in greater detail subsequently. from lnfusible resins. Reference to being soluble in 'an F r r ose of convenience, reference is simply made organic solvent means any of the usual organic solvents, atjthe moment to the following patents: U. S. Patent Nos. such as alcohols, ketones, esters, ethers, mixed solvents, 2,449,365; 2,499,366; 2,499,367; 2,499,368; and etc. Reference to "solubility is merely to difierentiate 2,499,370, all dated March 7, 1950, to De Groote and from a reactant which is not soluble and might be not Keis'er. 7

only nsoluble but also infusible. Furthermore, solu- "To illustrate the products useful in the process of the b lity is a factor insofar that it is sometimes desirable to present invention reference. will be made to a reaction dilute the compound containing the epoxy rings before involving a mole of the oxyalkylating agent, i. e., the comrea'ctmg with amino. In 'such instances, of course, the pound having two oxirane rings and oxyalkylated resins solvent selected would have to be one which is not susas described. Proceeding with the example previously ceptible to oxyalkylation, as, for example, kerosene, described it is obvious the reaction ratio of two moles of rings 'as depict'ed in the last formula preceding, or low Having obtained a reactant having generally '2 epoxy greases a product which may be indicated as follows:

(oxyalkylated resin) cance. However, molal ratios may be varied as noted subsequently.

Such products must be soluble in suitable solvents such as a non-oxygenated hydrocarbon solvent or an oxygenated hydrocarbon solvent, or for that matter, a mixture of the same with water. Needless to say, after the resin has been treated with a large amount of ethylene oxide the products are water soluble and may be soluble in an acid solution.

The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from relation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or at least distinct dispersibility in water. For instance, the products freed from any solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances water-soluble, in fact colloidally soluble.

Basic nitrogen atoms can be introduced into such derivatives by use of a reactant having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxy-propane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, we prefer to employ oxyalkylated derivatives, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have suificient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated derivatives obtained particularly by use of ethylene oxide, propylene oxide, etc., may not necessarily be xylenesoluble although they are xylene-soluble in a large number of instances. If such compounds are not xylenesoluble the obvious chemical equivalent, or equivalent chemical test, can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makesits presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

- Reference is made again to U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this text with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the wateriu-oil type, is characterized by the fact that a 50-50 solution in xylene, or its equivalent, when mixed with one to. three volumes of water and shaken will produce an emulsion.

For purpose of convenience what is said hereinafter will be divided into nine parts with Part 3, in turn, being divided into three subdivisions;

(oxyalkylated resin) in which the various characters have their prior signifi-' Part 1 is concerned with our preference in regard to the hydrophobe type of polyepoxide and particularly the hydrophobe type of diepoxide reactant, i. e., the one that enters into the formation of the intermediate ABA.

Part 2 is concerned with certain theoretical aspects of diepoxide prepared with the hydrophobe type, i. e., the one identified as Type B, preceding.

Part 3, Subdivision A, is concerned with the preparation of monomeric hydrophobe type diepoxides, including Table I. T

Part 3, Subdivision B, is concerned with the preparation of low molal hydrophobe type polymeric epoxides or mixtures containing low molal hydrophobe type polymeric epoxides or mixtures containing low molal hydrophobe type polymeric epoxides as well as the monomer and includes Table II.

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for low molal hydrophobe type diepoxide preparation.

Part 4 is concerned with suitable phenol-aldehyde resins to be employed for reaction with the epoxides.

Part 5 is concerned with the oxyalkylation of the previously described phenol-aldehyde resins.

Part 6 is concerned with the procedure involving preparation of an intermediate by reaction between 2 moles of the oxyalkylated phenol-aldehyde resin and one mole of the diglycidyl ether for example (identical with the products described in aforementioned co-pending application, Serial No. 343,804) followed by a second step in which 2 moles of these larger molecules are combined with use of a single mole of a diglycidyl ether or the like. This intermediate has been described previously as ABA.

Part 7 is concerned with suitable hydrophile nonaryl polyepoxides and particularly diepoxides employed as the reactant in uniting 2 moles of the intermediate ABA by means of a hydrophile epoxide and particularly a hydrophile diepoxide described as (C) to yield the final product described as ABACABA.

Part 8 is concerned with the reactions involving said intermediate ABA above-described and hydrophile po1yepoxides [C] to yield the final product indicated as ABACABA.

Part 9 is concerned with the resolution of petroleum emulsions of the Water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solvent-soluble liquids or low-melting solids. Indeed, they tend to form therm'osetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two ep'oxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co-generic mixture as explained subsequently. Preparation of the monomer;

or separation of the monomerfrom the remaining mass of the co-generic mixture is usually expensive. it mono mers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently, However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and'still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymersr It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances Where the phenolic nuclei are either united directly Without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. .All the various known classes may be use-d but our preference rests with these classes due to their availability and ease of preparation, 'and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other ep'oxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is H H H L H H E H I H Attention is again directed to the fact that. in the in-' stant part, to wit, Part 1, and insucceediug parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldchyde' or a ketonc. It would be immaterial if the divalent linking radical would be derived from theother groups illustrated" for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what, is said hereinafter, although directed to one class or a few classes,

applies with eoual force andefiect to the other classes of epoxide reactants. If sulfur-containing compounds are prepared they should be freed from impurities with considerable care 7 The polyepoxides and particularly the diep'oxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with alkali, of course, forms the epoxy ring. Anumber of problems are involved in attempting'to produce this compound free from cogeneric materials of related composition. The difiiculty stems from a number of sources and a few of the more important ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic soda or the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the following compounds:

(2) Even if one starts with the reactants in the preferred ratio, to Wit, two parts of epichlorohydrin to one part of bisphenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers, indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparently does, take place in connection with compounds having one, or in the present instance, two substituted oxirane rings, i. e., substituted 1,2 epoxy aaeaeee 9 l rings. Thus, in many ways it is easier to produce a For purpose of brevity, without going any further, the polymer, particularly a mixture of the monomer, dimer next formula is in essence one which, perhaps in an and trimer, than it is to produce the monomer alone. idealized way, establishes the composition of resinous (4) As has been pointed out previously, monoepoxides products available under the name of Epon Resins as may be present and, indeed, are almost invariably and 5 now sold in the open market. See, also, chemical paminevitably present when one attempts to produce polyphlet entitled Epon Surface-Coating Resins, Shell epoxides, and particularly diepoxides. The reason is the Chemical Corporation, New York city. The wordv one which has been indicated previously, together with Epon is a registered trademark of the Shell Chemical Corporation. (3H3 (')H (311: 5 1 O 04 0 (llHg CH: n 1 CH8 (IJHI on CH- C i CHg the fact that in the ordinary course of reaction a di- For the purpose of the instant invention, n may repreid h as sent a number including zero, and at the most a low CHI number such as 1, 2 or 3. This limitation does not exist H H H (L H H H in actual efforts to obtain resins as differentiated from HC -70-g0 3 O I the herein described soluble materials. It is quite prob 0 I o able that in the resinous products as marketed for coat-, 3 ing use the value of n is usually substantially higher. y react With a mole of his-Phenol A to give a 1110110- Note again what has been said previously that any for- P Y Indeed, in the Subsequent text immemula is, at best, an over-simplification, or at the most diately following reference is made to the dimers, trimers represents perhaps only the more important or principal and tetl'iimers in which two ePoxide groups are Present constituent or constituents. These materials may .vary Needless to y compounds can be formed which come from simple non-resinous to complex resinous epoxides SPOHd in every respect excePt that 0116 terminal epoxide which are polyether derivatives of polyhydric phenols group is absent and in its Place is a group having 011% containing an average of more than one poxide group Chlorine t and 0116 y y p, Or @156 two 3 per molecule and free from functional groups other than droxyl groups, or an unreacted phenolic ring. epoxide and hydroxyl groups.

some reference has been made Presence Referring now to what has been said previously, to of a chlorine atom and although all effort is directed i compounds h i b th an epoxy i th i towards the elimination of any chlorine-containing molelent a d ls a hydroxyl grou one need go no further cule yet it is apparent that this is often an ideal approach th t o id the ti product f rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group H H H H H H and a chlorine atom present. See U. S. Patent No. 40 C 7 2,581,464, dated January 8, 1952, to Zech. 0 L 0 What has been said in regard to the theoretical aspect is, of course, closely related to the actual method of and bisphenol A in a mole-for-mole ratio, since the preparation which is discussed in greater detail in Part 3, initial reactant would yield a product having an unparticularly subdivisions A and B. There can be no reacted epoxy ring and two reactive hydroxyl radicals. clear line between the theoretical aspect and actual Referring again to a previous formula, consider an expreparative steps. However, in order to summarize or ample where two moles of bisphenol A have been reillustrate what has been said in Part 1, immediately preacted with 3 moles of epichlorohydrin. The simplest ceding reference will be made to a typical example which compound formed would he thus:

DES n! (11H; o- -c 0- H-oH-oH (J-H (B C a 2-0 (I! 01 a 2 a OH: H: CH CH V I C a V \CH already has been employed for purpose of illustration. Such a compound is comparable to other compounds Th particular example is having both the hydroxyl and epoxy ring such as 9,10-

epoxy octadecanol. The ease with which this type of H H H l H H H compound polymerizes is pointed out by U. S. Patent No.

;-g-C $C g* 2,457,329, dated December 28, 1948, to Swern et al.

0 CH 0 The same difiiculty which involves the tendency to polymerize on the part of compounds having a reactive ring and a hydroxyl radical may be illustrated by com- It is obvious that two moles of such material combine readily with one mole of bis-phenol A,

0Ha pounds where, instead of the oxirane ring (1,2-epoxy HO & OH 7 ring) thereis present a 1,3-epoxy ring. Such compounds I are derivatives of trimethylene oxide rather than ethylene a 1 CH: oxide. See U. S. Patents Nos. 2,462,047 and 2,462,048, to produce the product which is one step further along, both dated February 15, 1949, toWyler.

tl a t a p ym I11 h 'W S, one At the expense of repetition of' what appeared p revi p'rior example-show the reaction product obtained from onsly, it may be well to recall that these materialsmay d id dflhe phenol A and two mo es CPiChI vary from simple soluble non-resinous to complex'non hydrin. 'This product in 'turn would represent three moles soluble resinous epoxides which are polyether derivatives of bisphenol A and tour moles of epichlorohydrin. of polyhydric phenols containing an average of more than 11 4 12 one epoxide group per molecule and free from functional PART 3 groups other than epoxide and hydroxyl groups. The subdivision A former are here included, but the latter, i. e., highly esin us or i 1 b1 t are The preparatlons of the drepoxy derivatives of the In summary th i li ht f h h been id, diphenols, which are sometimes referred to as diglycidyl pounds suitable for reaction with amines may be sumethers, have been described in a number of patents. F01

marized by the following formula: convenience, reference will be made to two only, to wit,

B! I IL! or for greater simplicity the formula could be restated aforementioned U. S. Patent 2,506,486, and aforemen- 5 Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. These particular compounds are described in the two patents just menin which the various characters have their prior significauce and in which R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a tloned.

TABLE I Ex- Patent ample Diphenol Diglycidyl ether refernumher enca C,H;(CH4OH):---.,., Di(epoxypropoxyphenyl)methane 2, 506, 486 CH;CH(CH40H),. Di(epoxypropoxyphenyl)methylmethane.-- 2, 506, 486 (CH3) :0 (OH40H);- Di (epoxypropoxyphenyl) dimethylmethane 2, 506, 486 C: 5 Di(epoxypropoxyphenyl)ethylmethylmethane-. 2, 506, 486 C2H5 2C (GGHAOH) L Dl(epoxypropoxyphenyl) diethylmethane 2, 506, 486 CHZC (C5111) (CGELOH Dl(eopxypropoxyphenyl)methylpropylmethane- 2, 506, 486 CH; (CeHa) (CH4OH)1. Di(epoxypropoxyphenyl)methylphenylmethane 2, 606. 486 0, 5C (C5Hs) (0 1140 11)," D1 (epoxypropoxyphenyl) ethylphenylmethane 2, 506, 486 E10 (CBHs) (CsHlOHhn Di(epoxypropoxyphenyl)propylphenylmethane- 2, 506, 486 C4H0C (C 115) (O6H4O Dl(epoxypropoxyphenyl)butylphenylmethane. 2, 506, 486 a H )2 Di(epoxypropoxyphenyl) tolylmethane 2, 508. 486 H3C H4) 0 (CH3) (O6H4OH)2- Di(epoxypropoxyphenyl) tolylrnethylmethane 2, 506, 486 Dihydroxy (it h 4,4-bis(2,3-epoxypropoxy) dipheuyl 2, 538,

nuclear hydrogen atom from the phenol 65 Subdivision B As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and I 7 particularly the aforementioned U. S. Patents Nos. in Ru and RH: rep s gnt and and carbon suhstituents of the aromatic n cl us, vsaid su v i lnil gh oii ic ement oncd U- S la e N 9- v2,57 1 8, cut member having not over 18 carbnn atoms; .1; reprethe iollowiug examples can be specified by reference to sents an integer selected from the class of zero and .1, and the formula therein provided one still bears in mind itris n'represents a whole number ;not vgreater than 3. in essence an ova-simplification.

TABLE I! H Q Q C-C-C 0R [R],.R10C(J--C -OR1[R],,RrO-C-C---O Hr H H2 H: J) H1 H H:

(in which the characters have their previous significance) Example R 0-- from HR1OH R-- n a 1: Remarks number a 1 Hydroxy h n n CH3 1 0,1,2 Phenol known as bis-phenol A. Low polymeric mixture about $6 or more where n'=0, remainder largely where l n=1, some where n==2. CH3

B2 410 CH: 1 0,1,2 Phenol known as bis-phenolB. See note ([2 regarding 131 above. (EH2 47H:

B3 Orthobutylphenol cm 1 0,1,2 Even though 11 is preferably 0, yet the usual reaction product might well contain materials where n is l, or to a 43 lesser degree 2. 7

B4..-...- Orthoamylphenol $11: 1 0,1,2 D0.

B5 Orthooctylphenol CH; 1 0,1,2 Do.

B6 Orthononylphenol CH: 1 0, 1,2 D0.

l CH:

B7 Orthododecylphenol YE; 1 0,1,2 Do.

138 Metacresol CH; 1 0,1,2 See prior note. This phenol used as initial material is known as bis-phenol O. For other suitable bis-phenols see A} U. 8. Patent 2,564,191.

B9 do CH; 1 0. 1, 2 See prior note.

B10 Dihuty (ortho-para) phenol. 1g 1 0.1.2 Do.

1311.-.-.. Diamyl (ortho para) phenol. ECI 1 0,1,2 Do.

B12 Dioctyl (ortho-para) phenoL 15 1 0,1,2 Do.

1813.-..-. Dinonyl (ortho-para) phenol. 13 1 0,1,2 Do.

BIL--- Diamyl (ortho-para) phenol. 1% 1 0,1,2 Do.

JJH;

me fin H 1 0,1,2 Do.

B16 Hydroxy benzene (1) 1 0,1,2 Do.

B17 Diamyl phenol (ortho-para) -SS 1 0,1,2 Do.

B15: do S 1 0. l. 2 Do. B19 Dib'utylphenol(ortho-para).- I 1g 1 0.1,2 Do.

Example R1O!rom HR OH -'R' n 1: Remarks number 1320.-..-. Dlbutylphenolortho-perm.... 1g 1g 1 0,1,2 See prior note.

B21 Dlnonylphenol(ortho-para). 162 g 1 0,1,2 Do.

B22 Hydroxy benzene (I? 1 0,1,2 Do.

1323 an N n 0 0,1,2 Do.

B24 Ortho-lsopropyl CH; 7 1 O, 1, 2 See prior note. As to preparation 014,4- lsopropylidene bls-(2-isopropylphenol) see U. S. Patent No. 2,482,748, dated Sept. 27, 1949, to Dietzler.

1325.....- Pare-oetyl CH;SCH, 1 0,1,2 Seepriornote. (As to preparation of the v phenol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeske. et al.)

1326-..... Hydroxybenzene CH1 1 v 0, 1, 2 See p'rlor note. (As to preparation of the phenol sulfide see U. S. Patent No. 2,526,545.)

JlsHs Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group of cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition: 7

HO- OH Other samples include:

OH @121 I (llH Rr-O wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and *R: is a substituent selected from the class consisting of alkyl, cyc'loalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms.

\ See U. S. Patent No. 2,515,907.

H (O C2H4) 9O CIHnUCHrOCtHn 7 051111 7 CsHn in which the C5H11 groups are secondary amyl groups.

See U. S. Patent No. 2,504,064.

CeHu (l'Ju ia Ho OH 7 See U. s. Patent No. 2,285,563.

H CgH/CEh 56 Cfia-t'i-OH: CH 6 a (3H2 00 R err-0E, o on, Hr-C 2 See U. s. Patent No. 2,503,196.

r-whejr'ein R is a member of the group consisting of allryl, .75 and alkoxy-alkyl radicals containing from '1 to 5 carbon '17 atoms, inclusive,- and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH I 2 R10- Rr 2 CH3 CH wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

CH=CH I OH OH |\C=OH l i H H3CCIJCH: sC-(f-CH;

CH3 CH3 See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

CaHn Cn u such as Alkyl Alkyl Alkyl R5 Alkyl in which R5 is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

0H CH3 OH; OH 1S={ Ra R1 R1 R2 in which R1 and R2 are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R1 and R2 each preferably contain 3 to about 10 carbcn atoms, and x is 1 to 4. The term sulfides" as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. ---Forthe present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. Patents: Nos. 2,499,365; 2,499,366; and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, described phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C14 carbon atom also being very satisfactory. The increased cost of the C16 and Cu: carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature, for instance, it has been stated that the composition is approximated in an idealized form by the formula OH OH OH H H l l R R R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

In the above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually, some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. The resin unit can be exemplified thus:

R R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation of resins, the kind herein employed as reactants, is well known. See U. S. Patent No. 2,499,368, dated March 7, 1950, to

r 19 DeGroote and Keiser. Resins can be made using-an c dupat ys s s tabf t O a t. W. 1 neither acid norbasic prgperties in the ordinary 'sense or without any catalyst at all, It is preferable that-the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong baseis used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly'in the presence of asmall amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 100th of a percent. Sometimes moderate increase in caustic sodaand caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i.e., one'having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture, for instance, oneapproximating4 phenolic nuclei will have some trirner and pentamer present. Thus, themolecular weight ,may be suchthat it corresponds to a fractional value for n, as for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purpose of convenience suitable resins are characterized in the following tablez .TABLE III Example R number Position of R Plienyl Para.

Tertiary butyl do Secondary butyl. Ortho. Gyclo-hexyl P Tertiary amyl Mixed secondary and tertiary amyl. Propyl Tertiary hexyl Octyl oicncncncn an Y Tertiary hutyl Tertiary amyl N onyl .1 Tertiary butyl Tertiary amyl Non Tertiary butyl Tertiary amyl Nonyl Tertiary butyl Tertiary amyl Nonyl Tertiary butyl.

Cyclo-hexyl ';,MQ ;-PQ fi 1l me be e e he Pa ent-s reared when, e .ox ihrla hst is giv n. thfiqn: siderable detail. See, for example, U. S. Patents 2,581,376; 2,581,377; 2,581,378; 2,581,379; 2,581,380, and 2,581,381, all datedlanuary 8, 1952, to De Groote and Keiser. As to further examples see U. S. Patent 2,602,052, dated July 1, 1952, to De Groote.

The oxypropylation or, for that matter, the treatment of resins with butylene oxide, glycide, or methylglycide, has been described in the first of the series in the above mentioned patents, i. e., those issuing'inol950.

Reference is made to U. S. Patent, 2,557,081, dated June 19, 1951; to De Groote and Keiser. This particular patent describes in considerable detail resins which are first treated with propylene'oxide and then with ethylene oxide or with ethylene oxide and then propylene oxide or with both oxides simultaneously.

In order to avoid an extensive repetition of What is already described in detail in the patent literature, we are referring to the table's beginning in' column 21 of U. S. Patent 2,581,376 and extending through column 36. We have simply numbered these products beginning with lb, allotting, of course, five numbers to each table beginning with the first table; For convenience these sixteen tables are summarized in the following table:

TABLE IV Sol- Ethyl- Ex. Phenol Aldehyde vent, Resin, ene N lbs. bs. oxide,

lbs

11).... Para-tertiary amyl..-. Formaldehyde.. 14. 25 15. 75 4. 00 21).. d0 d0 10. 90 12.10 15. 25 13 7. 93 19. 69 4. 25 l6. l5 2. 04 10. 2O 15. 00 3.00 10.00 9.

7. 27 13. 70 3. 15 8. 95 2. 10 8.00 15.80 3.25 12.40 12. 5O 7. 36 14. 00 4. 90 14. 80 4. 58 18. 52 16. 35 3. 00 12.00 10. 75 6. 58 10.85 4.90 13. 15 d0 3.72 13.43 Para-secondary butyl d 15. 55 4. 25 do 9. 17 16.00 5. 18 14. 25 4. 15 17.00 2.85 15. 17.20 2. 75

TABLE IV-Continued Sol- Ethyl- Ex. Phenol Aldehyde vent, Resin, ene No. lbs. lbs. oxide,

lbs.

66b Para-octyl Propionalde- 13. 30 16 90 3.

N OTEr-FOI ease of comparison blanks appear in the above table where afieaeee" blanks appear in previously mentioned tables in U. S. Patent 2,581,376.

As an illustration of oxypropylated resins involving the use of both ethylene and propylene oxide, reference is made to the aforementioned U. S. Patent 2,557,081, dated June 1, 1951, to De Groote and Keiser. The last table in column 28 of said patent describes in detail the preparation of a series of oxyalkylated resins in which both propylene and ethylene oxide are employed. Simply by way of illustration a series of 27 compounds are included, the descriptions of which appear in detail in said aforementioned U. S. Patent 2,557,081 to De Groote and Keiser.

TABLE VI See U. S. Pat.

Ex. No. Ex. N o.

in above patent Point on graph on above patent Ethylene oxide, lbs.

Propylene oxide, lbs.

' Flake can stie soda, ounces Resin used Wt. of

Resin,

lbs. xylene Hwqceoaolomcn i lQ JtdUOw t mamatjow W- iIiQ itdUQw z Tert. d

Tert. amyl phenol formaldlohyde. o

O::::::::: Nonyl phenol-formaldehyde.

butyl phenol iorm' a1 ehyde.

HP M m wwwgaocnf cma anbgaomr-dnk no on m an an Oxypropylated derivatives comparable to 1b through 80b as described above can readily be obtained by substituting a molar equivalent amount of propylene oxide, i. e., 56 lbs. of propylene oxide, for example, for each 44 lbs. of ethylene oxide. We have prepared such a similar series but for sake of brevity only a few will be included for purposes of illustration.

Note the first series of nine compounds, 1d through 9d, were prepared with a propylene oxide first and then ethylene oxide. The second 9, 10d through 18d inclusive, were prepared using ethylene oxide first and then propylene oxide, and the last 9, 19d through 27d, were prepared by random oxyalkylation, i. e., using a mixture of the two oxides.

TABLE V Ex- Oxypro- 801- Proample pylated Phenol Aldehyde vent, Resin, pylene N o. analog lbs. lbs. oxide,

lbs.

Para-tertiary amyl. Formaldehyde- 14. 15. 72 5. 10 do d0 10.90 12.10 19.40 7. l3 7. 93 25. 30 3. 84 4. 25 23. O0 1. 80 2. 04 13. 00 13. 30 16. 90 3.82 10. 20 12. 90 14. 6. 46 8. 24 21. 00 3. 86 4. 87 16. 6O 2. 94 3. 75 16. 80 12. 6O 16. 20 4. 46 9. 52 12. 24 16. 6. 8. 30 22. 6O 4. 25 5. 45 22. 00 2. 69 3. 43 18.

In the preparation of the resins our preference is to use hydrocarbon substituted phenols, particularly parasubstituted, in which the substituted radical R contains 4 to 18 carbon atoms and particularly 4 to 14 carbon atoms. The amount of alkylene oxide introduced may be comparatively large in comparison to the initial resin. For instance, there may be as much as 50 parts by weight of an oxide or mixed oxides used for each part by weight of resin employed.

It will be noted that the various resins referred toin the aforementioned U. S. Patent 2,499,370 are substantially the same type of materials as referred to in Table I. For instance, resin 3a of the table is substantially the same as 2a of the patent; resin 20a of the table is substantially the same as 34a of the patent; and resin 38a of the table is the same as 3a of the patent. V

In reaction with polyepoxides, and particularly diepoxides, a large number of the previously described oxyalkylated resins have been employed. For convenience, the following list is selected indicating the previously described compounds and their molecular weights. Such resins are generally employed as a 50% solution and the polyepoxide employed is a 50% solution, usually both reactants being dissolved in xylene and sulficient sodium methylate added to act as a catalyst, for instance, 1 to 2%. 7

TABLE VII Example Molecular number weight;

112 1, 202 2b 2, 169 3b 3, 339 4b 4, 609 5b 5, 749 6b 1, 509 7b 2, 466 8b 3, 657 9b 5, 867 10b 6, 087 1c 1, 270 2c 2, 494 3c 4, 019 4c 6, 139 5c 7, 079 1d 1, 697 2d 1, 918 3d 3, 189 4d 23, 959 5d 23, 959 6d 24. 909 7d 23, 959 8d 91s 9d 1, 697

PART 6 place in substantially the same way, i. e., by the oppor-.

tunity to react at somewhere above the boiling point of water and below the point of decomposition, for example, 130-185 C. in the presence of a small amount of alkaline catalyst. Since the polyepoxide is non-volatile as compared, for example, with ethylene oxide, the reaction is comparatively simple. Purely from a mechanical standpoint it is a matter of convenience to conduct both classes of reactions in the same equipment. In other words, after the phenol-aldehyde resin has been reacted with ethylene oxide, propylene oxide or the like, it is subsequently reacted with a polyepoxide.

The polyepoxide reaction can be conducted in an ordinary reaction vessel such as the usual glass laboratory equip- 24 ment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365. One can use a variety of catalysts in connection with the polyepoxide of the same 'class employed with monoepoxide. In fact, the reaction will go at an extremely slow rate without any catalyst at all. alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chlorides; Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. For practical purposes, it is best to use the same catalyst as is used in the initial oxyalkylation step and in many cases there is sufficient residual catalyst to serve for the reaction involving the second oxyalkylation step, i. e., the polyepoxide. For this reason, we have preferred to use a small amount of finely divided caustic soda or sodium methylate as the initial catalyst and also the catalyst in the second stage. The amount generally employed is 1, 2, or 3% of these alkaline catalysts.

Actually, the reactions of polyepoxides with various resin materials have been thoroughly described in the literature and the procedure is, for all purposes, the same as with glycide which has been described previously.

It goes without saying that the reaction involving the polyepoxide can be conducted in the same manner as the monoepoxide as far as the presence of an inert solvent is concerned, i. e., one that is not oxyalkylation-susceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained frompetroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The solvent so selected should be one which, of course, is suitable in the oxyalkylation step involving the monoepoxides described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required. Here again it has been our preference to have a solvent present in the oxyalkylation involving the initial stage and permitting the solvent to remain. The amount of solvent may be insignificant, depending whether or not exhaustive oxyalkylation is employed, However, since the oxyalkylated phenol-aldehyde resins are almost invariably liquids there is no need for the presence of a solvent as when oxyalkylation involves a solid which may be rather high melting. Thus, it is immaterial whether there is a solvent present or not and it is immaterial whether solvent was added in the first stage of oxyalkylation or not, and also it is immaterial whether there was solvent present in the second stage of oxyalkylation or not. The advantage of the presence of solvent is that sometimes it is a convenient way of controlling the reaction temperature and thus in the subsequent examples we have added sufficient xylene so as to produce a mixture which boils somewhere in the neighborhood of to C. and removes xylene so as to bring the boiling point of the mixture to about 140 C. during part of the reaction and subsequently removing more xylene so that the mixture refluxed at somewhere between to C. This was purely a convenience and need not be employed unless desired.

Example la The oxyalkylated resin employed was-the one previously identified as 2b, having a molecular weight of 2169; the amount employed was 217 grams. The resin was dissolved in approximately an equal weight of xylene. The mixture was heated to just short of the boiling point of water, i. e., a little below 100 C. Approximately one-half percent of sodium methylate was added, or,

more exactly, 1.1 grams. The stirring was continued.

The usual catalysts include" 25 until there was a solution or distribution of the catalyst. The mixture was heated to a little past 100 C. and left at this temperature while 17 grams of the diepoxide (previously identified as 3A), dissolved in an equal weight of Xylene, were added. After the diepoxide was 26 stant invention. More' specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll et al.; and U. S. Patent No. 2,581,464,

. added the temperature was permitted to use to approxidated January 8, 1952, to Zech. The simplest d1epox1de mately 107 C. The time required to add the diepoxide is probably the one derived from 1,3-butadiene or iso- Was approximately one-half hour. The temperature rose prene. Such derivatives are obtained by the use of perin this period to about 125 C. The temperature rise oxides or by other suitable means and the diglycidyl ethers was controlled by allowing the xylene to reflux over and may be indicated thus: to separate out the xylene by a phase separating trap. H H H H In any event, the temperature was raised shortly to 138- HCCOOH 140 C. and allowed to reflux at this temperature for almost three hours. Tests indicated that the reaction 1 CH, was complete at the end of this time; in fact, it probably n H n was complete at a considerably earlier stage. The xylene HC -COH which had been separated out was returned to the mixture so that the reaction mass at the end of the pro- 0 O cedure represented about 50% reaction product and 50% In some instances the compounds are essentially solvent. The procedure employed is, of course, simple 2O derivatives of etherized epichlorohydrin or methyl epiin light of what has been said previously; in fact, it chlorohydrin. Needless to say, such compounds can be corresponds to the usual procedure employed in connecderived from glycerol monochlorohydrin by etherization tion with an oxyalkylating agent such as glycide, 1. e., a prior to ring closure. An example is illustrated in the non-volatile oxyalkylatmg agent. At the end of the repreviously mentioned Italian Patent No. 400,973; action period the mass obtained was a dark viscous mix- OH CH CH O-OIEI CHCH ture. It could be bleached, of course, by use of charcoal, 2 z a filtering earths, or the like. 0 I 0 Various examples obtained in substantially the same Another type of diepoxlde is diisobutenyl dioxide as manner as employed are described in the following table: described in aforementioned U. S. Patent No. 2,070,990,

TABLE VIII Oxyalkyl- Amt., Diepoxide Amt, Catalyst Xylene, Molar Time of Max. Ex. No. ated gms. used gms. (NaOCHg), gms. ratio reaction, temp., Color and physical state resin grams hrs. C.

217 3A 17 1.1 234 2:1 3 140 Dark, viscous mass. 400 3A 17 2.4 477 2:1 4 145 Do. 247 3A 17 1. 3 254 2: 1 3 150 Do. 509 3A 17 3. 1 025 2: 1 4 145 Do. 249 3A 17 1. s 255 2: 1 2. 5 150 Do. 402 3A 17 2. 0 419 2: 1 4 145 Do. 708 3A 17 3. 0 725 2: 1 5 152 Do. 192 3A. 17 1. 0 209 2: 1 2. 5 142 Do. 319 8A 17 1. 0 330 2: 1 3 147 Do. 249 3A 17 1. 2 250. 7 2: 1 3 155 Do. 217 B1 27. 5 1. 2 244. 5 2: 1 s. 5 145 D0. 450 B1 27. 5 2. 4 487. 5 2:1 4 150 Do. 247 131 27.5 1. 3 274. 5 2: 1 4 152 Do. 000 B1 27.5 3.1 636. 5 2: 1 5 158 Do. 249 B1 27. 5 1. 3 27s. 5 2:1 4 146 Do. 402 B1 27.5 1. 2 429. 5 2: 1 5 150 Do. 703 B1 27.5 2. 0 735. 5 2: 1 5 152 Do. 192 B1 27. 5 1. 0 219. 5 2: 1 3. 5 148 Do. 319 B1 27.5 1. 7 345. 5 2:1 4 150 Do. 249 B1 2. 8 1. 2 251.8 2:1 3 152 Do.

dated February 16, 1937, to Groll, and is of the follow- TABLE IX ing formula:

Prob. mol. Amount of Amount of Ex. No. Oxyallrylweight of product, solvent H20 C CH2 CH2 C CH2 ated resin reaction grams grams used product OH: H3

4, 680 4 680 2,340 The diepoxldes previously described may be Indicated by 9,540 4,770 2, 325 the following formula: 5, 280 5, 280 2. 640 I I 12, 520 5,250 3,150 H R H r H 5. 320 5,330 2, 570 H 8,380 8.370 4.180 n 122 52 O 0 4,180 6,720 6, 720 3.360 1n which R represents a hydrogen atom or methyl radi- 160 M16 2508 cal and R" re resents the divalent radical uniting the two 4, 890 4, 890 2, 445 I? 7 9,750 4,880 2, 440 terminal epoxrde groups, and n is the numeral 0 or 1. %;38 3 51 33 As previously pointed out, in the case of the butadiene 5, 530 5. 540 Z, derivative, n is 0. In the case of diisobutenyl dioxide ,2522 3 R is CH2CH2 and n' is 1. In another'example pre- .390 @338 3% viously referred to R" is CHzOCI-Ia and'n' is 1; v 1 38 5 2:520 However, for practical purposes the only diepoxide 70 available in quantities other than laboratory quantities PART 7 is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which'is Reference is made to various patents to illustrate the largely acyclic diglycerol, and epichlorohydrin or equivmanufacture of the non-aryl hydrophile polyepoxides and alent thereof, in that the epichlorohydrin itself may supparticularly diepoxides employed as reactants in the inply the glycerol or diglycerol radical in addition-to the areas epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R1 is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which or more carbon atoms are united in a single uninterrupted single group. R1 is inherently hyis derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus,R(OH)n, where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes ,polyepoxides if actually derived, or

theoretically derived at least, from Water-insoluble diols l or Water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts Referring to a compound of the type above in the formula in which R1 is C3H5(OH), it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide, or, similarly, if R happened to be C3H5(OH)OC3H5(OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterruptedchain. This particular diglycidyl ether is obtained by the use 7 of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of 'epichlorohydrin'so astogivethe appropriate diepoxide.

The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds, is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom, and thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2.0xygen atoms, are obtainable by the conventional reaction of combining erythritol with carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, fol-lowed by conversion of the terminal hydroxyl ,groups into epoxy radicals. See also Canadian Patent 7 PART 8 As pointed out previously, the reaction described in Part 6, preceding, resulted in an intermediate which was described thus: (A-BA). The reaction described in the instant part has'been indicated thus:

. The manufacturing procedure is, of course, merely a continuation of what has been described previously in Part 6 and it is simply a switch from the one type of polyepoxide to the other. Of course, after the hydrophobe polyepoxide is added, sufficient time should pass to insure completeness of reaction before adding the hydrophile type. For purpose of illustration, however, the following examples are included:

Exalmple 1g diepoxide was then added slowly over a period of less than a half-hour. The temperature was raised to C. and held at this temperature for about 2 hours. product obtained was a dark viscous mass when the sol vent was evaporated. On completion of the reaction enough acetic acid was added to neutralize the catalyst. In a second series of derivatives, hydrophile diepoxide B The was employed. Both have been describedpreviously in Part 7 preceding.

The data are summarized in hereto appended Tables X and XI.

. 36 consisting of (a) compounds where the phenolic nuclei are directly joined Without an intervening bridge radical, and (b) compounds containing a radical in which two phenolic nuclei are joined by a divalent radical selected TABLE X Polyepoxide Catalyst Time of Max.

Ex. derived Amt, Diepox- Amt, (NaOCH Xylene, Molar reaction, temp., Color and physical state No. intergms. ide used gms. gms. gms. ratio hrs. C.

mediate product 234 A 9. 3 2. 4 243 2:1 2 140 Dark viscous mass. 477 A 9. a 4. 8 486 211 2 142 Do. 264 .4 9. 3 2. 7 273 2: 1 2 145 Do. 250 A 3. 7 2. 5 254 2:1 2 140 Do. 266 A 9. 3 2. 7 275 2=1 2 140 Do. 419 A 9. a 4. 2 428 211' 2 145 Do. 290 A 3. 7 2. 9 294 2: 1 2 145 D0. 209 A 9. 3 2.1 218 2:1 2 140 Do. 336 A 9. 3 8. 4 243 211 2 147 Do. 501 A 1. 9 5. 503 2:1 2 150 Do. 234 B 5. 5 2. 4 240 2:1 2 150 Do. 477 B 5. 5 4.8 283 2: 1 2 145 Do. 264 B 5. 5 2. 7 270 2:1 2 147 Do. 250 B 2. 2 2. 5 252 2: 1 2 146 Do. 266 B 5. 5 2. 7 272 2: 1 2 145 D0. 410 B 5. 5 4. 2 425 2: 1 2 140 Do. 290 B 2. 2 2. s 292 2; 1 2 145 D0. 209 B 5. 5 2.1 215 211 2 146 Do. 336 B 5. 5 8. 4 342 2: 1 2 150 Do. 501 B 1.1 5. 0 502 2:1 2 145 D0.

from the class consisting of ketone residues formed by TABLE X1 the elimination of the ketonic oxygen atom, and aldehyde resldues obtained by the elimination of the aldehyde oxygen atom, the divalent radical Oxyalkyl- Probable Amount of Amount of H H Ex.No. ated resin molecular product, solvent -CC- used twnof rgac-t grams grams H H 10H TO 110 p the divalent r I I n 3 33 312 2 radical, the divalent sulfone radical, and the divalent 17,130 3, 1,713 monosulfi radical S- l 29,370 2%? g 1 y de the diva ent radical 8,730 5 13, 810 2,762 1,381 40 CH2SCH2- 100, 600 4, 028 2, 014

gggg 5,322 %ggg and the divalent dlsulfide radical SS; said phenolic 111200 2:240 1:120 portion of the diepoxide being obtained from a phenol 25, 680 5, 568 of the structure 11, 280 2, 256 1, 128 17,400 3, 480 1,740 40 20. 640 5, 928 2, 964 0B PART 9 In Which R, R, and R represent a member of the As to the use of conventional demulsifying agents, reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applied with equal force and efiect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 1g, herein described.

Having thus described our invention, What We claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products (ABACABA); said synthetic hydrophile products being obtained by a two-step process, the first step involving an intermediate (ABA) which, in turn, represents the reaction products of (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a phenolic polyepoxide free from reactive functional groups other than epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; said oxyalkylated phenol-aldehyde resins, reactant (A) being the products of oxyalkylation of (aa)- an'alpha-beta alkylene oxide having not more than 4 carbon atoms and'selccted from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (552) an oxyalkyla tion-susce'ptible fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehhyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of 31 divalent radicals having the formula (R10)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin bycweight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermo'setting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of oxyalkylationand acylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; said second step being the reaction product between 2 moles of the aforementioned intermediate (ABA) and one mole of (C) a non-aryl hydrophile polyepoxide characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom V is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterizedby the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said final product being a member of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that'the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (ABA) and (C) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products (ABACABA): said synthetic hydrophile products being obtained by a two-step process, the first step involving an intermediate (ABA) which, in turn, represents the reaction products of (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a member of the class consisting of (1) compounds of the following formula:

H: H H; By

I OH

H H C C 11 E the divalent II C radical, the sulfone radical, and the divalent monosulfide radical S, the divalent radical CH2SCH2-, and the divalent disulfide radical S-S- and R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol III 0 including monoepoxides; said oxyalkylated phenol aldehyde resins, reactant (A), being the products derived by oxyalkylation of (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (bb) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a pluralitylof divalent radicals having the formula (R20)n", in which R2 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n" is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) to'one'in'ole (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of n'on-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of oxyalkylation- 5 reaction product between 2 moles of the aforementioned intermediate (ABA) and one mole of (C) a n'on-aryl hydrophile polyepoxide characterized by the fact that the precurs'ory polyhydric alcohol, in which an oxygenlinked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said p-olyepoxides being free from reactive functional groups other than References Cited in the file of this patent (C) being conducted below the pyrolytic point of the 10 2,615,853

reactants and the resultants of reaction.

UNITED STATES PATENTS Beck et a1. Nov. 23, 1948 Bock et a1 Nov. 23, 1948 De Groote et a1. Mar. 7, 1950 Keiser et a1. May 16, 1950 Landa June 26, 1951 De Groote July 1, 1952 Kirkpatrick et a1 Oct. 28, 1952 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS (ABACABA); SAID SYNTHETIC HYDROPHILE PRODUCTS BEING OBTAINED BY A TWO-STEP PROCESS, THE FIRST STEP INVOLVING AN INTERMEDIATE (ABA) WHICH, IN TURN REPRESENTS THE REACTANT PRODUCTS OF (A) AN OXYALKYLATED PHENOL-ALDEHYDE RESIN CONTAINING A PLURALITY OF ACTIVE HYDROGEN ATOMS, AND (B) A PHENOLIC POLYEPOXIDE FREE FROM REACTIVE FUNCTIONAL GROUPS OTHER THAN EPOXY AND HYDROXYL GROUPS, AND COGENERICALLY ASSOCIATED COMPOUNDS FORMED IN THE PREPARATION OF SAID POLYEPOXIDES; SAID EPOXIDES BEING MONOMERS AND LOW MOLAL POLYMRS NOT EXCEEDING THE TETRAMERS; SAID EPOXIDES BEING SELECTED FROM THE CLASS CONSISTING OF (A) COMPOUNDS WHERE THE PHENOLIC NUCLEI ARE DIRECTLY JOINED WITHOUT AN INTERVENING BRIDGE RADICAL, AND (B) COMPOUNDS CONTAINING A RADICAL IN WHICH TWO PHENOLIC NUCLEI ARE JOINED BY A DIVALENT RADICAL SELECTED FROM THE CLASS CONSISTING OF KETONE RESIDUES FORMED BY THE ELIMINATION OF THE KETONIC OXYGEN ATOM, AND ALDEHYDE RESIDUES OBTAINED BY THE ELIMINATION OF THE ALDEHYDE OXYGEN ATOM, THE DIVALENT RADICAL 